KR101858771B1 - Polyurethane having high light refraction - Google Patents

Abstract

The present invention relates to the use of solventless low-monomer polyisocyanates based on araliphatic diisocyanates in the manufacture of light-resistant and weather-resistant polyurethane bodies with high light refraction and low dispersion.

Description

POLYURETHANE HAVING HIGH LIGHT REFRACTION [0002]

There is known a method of producing a light resistant weatherable plastic by reacting an aliphatic or cycloaliphatic polyisocyanate with a compound containing a hydrogen atom. Depending on the nature of the H-acid reactive partner such as polyols, polyamines and / or polythiols, for example, heavier products having urethane, urea and / or thiourethane structures are formed.

In addition, the generic term " polyurethane " is used hereinafter synonymously for a number of different polymers which may be prepared from polyisocyanates and H-acid compounds.

There is an increasing interest in light-resistant polyurethane compositions that are transparent to the marketplace, for example, as lightweight alternatives to mineral glass for manufacturing glazing for automotive and aircraft structures, or as embedded compositions for optical, electronic or optoelectronic components Are recorded.

In high performance optical applications, particularly in lenses or spectacle lenses, plastic materials having generally high optical refraction and low dispersion (high Abbe number) are required.

Methods for producing transparent polyurethane compositions with high light refraction have already been frequently disclosed in the literature. In principle, in this context so-called araliphatic diisocyanates, i.e. diisocyanates in which the isocyanate groups are bonded to the aromatic system via aliphatic radicals, are used as the polyisocyanate component. Due to its aromatic structure, araliphatic diisocyanates provide polyurethanes with high refractive indices, while at the same time the aliphatically bonded isocyanate groups ensure the lightfastness and low yellowing tendency required for high performance applications.

For example, US-A 4 680 369 and US-A 4 689 387 disclose polyurethanes and polythiourethanes suitable as lens materials, in which a specific sulfur-containing polyol or mercapto-functional aliphatic compound (Isocyanatomethyl) benzene (m-xylylene diisocyanate, m-XDI), 1,4-bis (isocyanatomethyl) benzene Tetramethylxylylene diisocyanate, m-TMXDI) or 1,3-bis (2-isocyanatophenyl) (Isocyanatomethyl) -2,4,5,6-tetrachlorobenzene to achieve a particularly high refractive index.

Al aliphatic diisocyanates such as m- and p-XDI or m-TMXDI are also disclosed in many other publications such as EP-A 0 235 743, EP-A 0 268 896, EP-A 0 271 839, EP-A 0 408 459 , EP-A 0 506 315, EP-A 0 586 091 and EP-A 0 803 743 as polyisocyanate components which are preferred for the manufacture of high refractive lens materials. Here, the araliphatic diisocyanate serves as a cross-linking agent component for the polyol and / or the polythiol and, depending on the reaction partner, provides a transparent plastic having a high refractive index in the range of 1.56 to 1.67 and a relatively high Abbe number of up to 45.

However, all the processes for preparing highly photorefractive polyurethane compositions used in the aforementioned optical applications use aliphatic diisocyanates which are high amounts of low molecular weight monomers, but such diisocyanates are health hazardous and, in some cases, There is a considerable problem in common that they are classified as sensitive or even toxic agents with high vapor pressures. The processing of such monomeric diisocyanates requires high costs in terms of safety for reasons of industrial hygiene. Moreover, as has been proposed, for example, in EP-A 0 235 743 or EP-A 0 506 315, when an excess of polyisocyanate is used, the unreacted monomer diisocyanate remains in the molded part, It is also possible to gradually evaporate from the parts.

The main reason for using an araliphatic diisocyanate in monomer form is that the known low-monomer derivative of the diisocyanate exhibits an extremely high viscosity at room temperature, and is generally itself used for conventional solventless applications, This is because it is a solid compound that has been considered to have not been used. Thus, low-monomer polyisocyanates based on araliphatic diisocyanates are used solely as solutions in organic solvents, for example in lacquers, adhesives or printing inks.

It is therefore an object of the present invention to provide a novel high transparency polyurethane composition that is stable to light and weathering, has high light refraction and low dispersion, and does not have the disadvantages of known systems. The novel polyurethane compositions should be based on toxicologically acceptable raw materials and can be prepared by conventional methods, for example by simple manual injection or by means of suitable machines, for example by RIM processes, It should be possible to provide highly crosslinked transparent molded articles in applications.

This object is achieved by providing a polyurethane which will be described in detail below.

DETAILED DESCRIPTION OF THE INVENTION The present invention, which is described in detail below, is based on the fact that the viscosity of a solventless low-molecular polyisocyanate based on an aliphatic diisocyanate which is extremely high in viscosity or even solid at room temperature is slowly heated to a relatively mild temperature, Based on the unexpected finding that it is possible to provide a light-resistant, non-sulfur-modified polyurethane body characterized by high light refraction and high Abbe number at the same time lowering to such an extent that it can be processed without problems under normal conditions. This finding has never been anticipated, for example because the low-monomer polyisocyanates based on cycloaliphatic or aromatic diisocyanates which are solid in the solvent-free form, have a softening point in the range significantly higher than 80 ° C Because it is known to have a melting point.

For example, in EP-A 0 329 388 and EP-A 0 378 895, the technical background is a method for producing a lens of polythiourethane or polyurethane plastic, which enumerates a large list of diisocyanates which may be suitable as binder components Specific examples thereof include aliphatic diisocyanates such as XDI, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, TMXDI, bis (isocyanatobutyl) benzene, bis (Isocyanatomethyl) naphthalene or bis (isocyanatomethyl) diphenyl ether, and the aforementioned diisocyanate prepolymer, urethane, carbodiimide, urea, buret, dimer and trimer Although it is generally pointed out that suitable starting polyisocyanates are suitable for use in the present invention, It can not be inferred at all from the fact that it suggests precisely that the cator aliphatic polyisocyanate is particularly suitable for the production of plastic compositions having a high refractive index. Rather, the embodiments of these publications are entirely carried out using monomeric diisocyanates such as m-XDI and m-TMXDI.

The present invention relates to a process for the preparation of light-resistant, compression-molded or foamed polyurethane bodies from a solventless polyisocyanate component A) formed from two or more araliphatic diisocyanate molecules and having an isocyanate group content of 10 to 22% by weight and a monomeric diisocyanate content of less than 1.0% As well as the use thereof.

In addition,

A) a polyisocyanate component formed from two or more araliphatic diisocyanates and having an isocyanate group content of 10 to 22% by weight and a monomeric diisocyanate content of less than 1.0%

and,

B) a reaction partner which is reactive towards isocyanate groups and has an average functionality of from 2.0 to 6.0, and optionally

C) Additional auxiliaries and additives

By the absence of the solvent,

A method for producing a light-resistant polyurethane composition while maintaining an equivalence ratio of isocyanate group to isocyanate-reactive groups at 0.5: 1 to 2.0: 1.

Finally, the present invention provides a transparent compacted or foamed article produced from a light-resistant polyurethane composition obtainable in this way.

Wherein the polyisocyanate component A) comprises a urethane dione, isocyanurate, iminooxyadiazin dione, urethane, allophanate, burette and / or oxadiazinetrione groups and has a solid form at 23 ° C, Polyisocyanate based on an araliphatic diisocyanate having a viscosity of from 10 to 22% by weight and a monomeric aliphatic diisocyanate content of less than 1.0% by weight.

The araliphatic starting diisocyanates suitable for preparing the polyisocyanate component A) are any desired diisocyanates, the isocyanate groups of which are optionally joined to the aromatic further optionally substituted through an aliphatic radical which is branched, for example 1,3-bis (Isocyanatomethyl) benzene (m-xylylene diisocyanate, m-XDI), 1,4-bis (isocyanatomethyl) benzene (p-xylylene diisocyanate, p- Tetramethylxylylene diisocyanate, m-TMXDI), 1,4-bis (2-isocyanatopropane-2-yl) Benzene (p-tetramethylxylylene diisocyanate, p-TMXDI), 1,3-bis (isocyanatomethyl) -4-methylbenzene, 1,3-bis (isocyanato methyl ) -4-ethylbenzene, 1,3-bis (isocyanatomethyl) -5-methylbenzene, 1,3-bis (isocyanatomethyl) , 1,4-bis (isocyanatomethyl) -2,5-dimethylbenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6-tetramethylbenzene, 1,3- Bis (isocyanatomethyl) -5-tert-butylbenzene, 1,3-bis (isocyanatomethyl) -4-chlorobenzene, 1,3-bis (isocyanatomethyl) - dichlorobenzene, 1,3-bis (isocyanatomethyl) -2,4,5,6-tetrachlorobenzene, 1,4-bis (isocyanatomethyl) -2,3,5,6- (Isocyanatomethyl) -2,3,5,6-tetrabromobenzene, 1,4-bis (2-isocyanatoethyl) benzene, 1,4- Bis (isocyanatomethyl) naphthalene, and any desired mixtures of such diisocyanates.

The process for preparing the polyisocyanate component A) from the araliphatic diisocyanate can be carried out by conventional methods used for oligomerization of diisocyanates, for example Laas meat al ., J. Prakt . Chem . 336, 1994, 185-200 ), and subsequently the unreacted monomer diisocyanate is removed by distillation or extraction. Specific examples of low-monomer polyisocyanates of araliphatic diisocyanates can be found, for example, in JP-A 2005161691, JP-A-2005162271 and EP-A 0 081 713.

Preferred polyisocyanates A) are those having uretdione, allophanate, isocyanurate, iminooxyadinedione and / or buret structure.

It is particularly preferred that the polyisocyanate A) is a polyisocyanate of the above type based on m-XDI, p-XDI and / or m-TMXDI having an isocyanate group content of 11 to 21.5% by weight and a monomer diisocyanate content of less than 0.8% .

It is very particularly preferred that the polyisocyanate of component A) is a polyisocyanate of the above type based on m-XDI having an isocyanate group content of 15 to 21% by weight and a monomer m-XDI content of less than 0.5%.

The araliphatic starting diisocyanates used to prepare the polyisocyanate component A) can be prepared by any desired method, for example by phosgenation on a liquid or gaseous phase, or by a phosporane pathway, such as urethane decomposition.

The low-monomer polyisocyanate A) is in principle a substantially colorless solid resin having a viscosity of more than 150,000 mPas at 23 DEG C and an isocyanate group content of 11 to 21% by weight, preferably 15 to 21% by weight And the average isocyanate functionality thereof is preferably 2.2 to 5.0, particularly preferably 3.0 to 4.5. Polyisocyanate A) has fewer residual monomers because the residual content of monomeric aliphatic diisocyanates is less than 1.0% by weight, preferably less than 0.8% by weight, particularly preferably less than 0.5% by weight.

In order to prepare the light-resistant polyurethane composition according to the present invention, the polyisocyanate A) is reacted with an isocyanate group and has an average functionality of 2.0 to 6.0, preferably 2.5 to 4.0, particularly preferably 2.5 to 4.0, 3.5 with any desired solventless reaction partner B).

Such reaction partners specifically include polyether polyols, polyester polyols, polyether-polyester polyols, polythioethers, polyether polyols, polyether polyols, polyether polyols, polyether polyols, polyether polyols, polyether polyols, Polyether polyols, polymer-modified polyether polyols, graft polyether polyols, especially those based on styrene and / or acrylonitrile, polyether-polyamines, hydroxyl group-containing polyacetals and / Polycarbonate. For suitable reaction partners B), see, for example, N. Adam et al .: "Polyurethanes", Ullmann's Encyclopedia of Industrial Chemistry, Electronic Release, 7th ed., Chap. 3.2-3.4, Wiley-VCH, Weinheim 2005 ].

Suitable polyether polyols B) are described for example in DE-A 2 622 951, column 6, line 65 to column 7, line 47, or line EP-A 0 978 523, , Where they correspond to those previously described in terms of functionality and molecular weight. Particularly preferred polyether polyols B) are adducts of ethylene oxide and / or propylene oxide on glycerol, trimethylol propane, ethylenediamine and / or pentaerythritol.

Suitable polyester polyols B) are of the type mentioned, for example, in EP-A 0 978 523, line 5, lines 17 to 47 or EP-A 0 659 792, page 6, lines 8 to 19, , Where they correspond to those previously described, preferably those with a hydroxyl value of 20 to 650 mg KOH / g.

Suitable polythiophenols B) are, for example, condensation products of known thiodiglycol or thiodiglycol with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids and / or aminoalcohols. Depending on the properties of the mixture components used, they are polythio-mixed ether polyols, polythioether-ester polyols or polythioether-ester-amide polyols.

Suitable polyacetal polyols as component B) are, for example, simple glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxyethoxydiphenyldimethylmethane (adduct of 2 mol ethylene oxide on bisphenol A) Or the known reaction products of hexanediol and formaldehyde, or polyacetals prepared by polycondensation of cyclic acetals such as trioxane.

A mixture of aminopolyethers or aminopolyethers, i.e., groups reactive with isocyanate groups (at least about 50 equivalent%, preferably at least about 80 equivalent% of primary and / or secondary, aromatic or aliphatic bonded amino groups, And the remaining component is composed of primary and / or secondary aliphatic-bonded hydroxyl groups) is particularly suitable as component B). Examples of such suitable aminopolyethers are those mentioned in EP-A 0 081 701, column 4, line 26 to column 5, line 40. The amino functional polyether-urethane or urea can be prepared, for example, by hydrolysis of an isocyanate functional polyether prepolymer by the method of DE-A 2 948 419, or by reacting a polyester in the above molecular weight range containing amino groups Is also suitable as starting component B).

Examples of other suitable components B) which are reactive towards isocyanate groups are the specific polyols disclosed in EP-A 0 689 556 and EP-A 0 937 110, which are, for example, epoxidized fatty acid esters and epoxides of aliphatic or aromatic polyols Can be obtained by a ring opening reaction.

Polybutadiene containing hydroxyl groups may also be used as component B).

In addition, component B) which is suitable for the preparation of polyurethane compositions which are reactive towards isocyanate groups and which have a very high photorefractive index, are particularly preferably polythio compounds such as simple alkanethiols such as methanedithiol, 1,2-ethanedithiol , 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3- , Pentanedithiol, 1,6-hexanedithiol, 1,2,3-propanetriethiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2- 1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol and 2-methylcyclohexane-2,3-dithiol, thioether group-containing polythiol such as 2,4-dimercapto Methyl-1,5-dimercapto-3-thiapentane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl- Dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiane (Mercaptoethylthio) -1,10-dimercapto-cyclohexanecarboxylate, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,5- Tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,5,5-tetrakis (mercaptomethylthio 3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2-mercaptoethylthio-1,3-dimercaptopropane, (Mercaptoethylthio) -1-mercaptopropane, 2,2-bis (mercapto) -1,3-dimercaptopropane, bis (mercaptomethyl) sulfide, bis (mercaptomethyl) (Mercaptoethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (Mercaptomethylthio) methane, bis (mercaptoethylthio) methane, tris (mercaptoethylthio) methane, bis (Mercaptomethylthio) ethane, 1,2-bis (mercaptoethylthio) ethane, 1,3-bis (mercaptomethylthio) (Mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris , 3-tris (mercaptopropylthio) propane, tetrakis (mercaptomethylthio) methane, tetrakis (mercaptoethylthiomethyl) methane, tetrakis (mercaptopropylthiomethyl) 1,4-dithiane, 2,5-bis (mercaptomethyl) -1,4-dithiane and their oligomers obtained according to JP-A 07118263, 1,5-bis (mercaptopropyl) Dithiane, 1,5-bis (2-mercaptoethylthiomethyl) -1,4-dithiane, 2-mercaptomethyl-6-mercapto-1,4-dithiacycloheptane, 2,4,6-trimercapto-1,3,5-trithiane, 2,4,6-trimercaptomethyl-1,3,5-trithiane and 2- (3-bis 2-thiopropyl) -1,3-dithiolane, polyester thiol such as ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), diethylene glycol (2-mercaptoacetate), diethylene glycol (3-mercaptopropionate), 2,3-dimercapto-1-propanol (3-mercaptopropionate) -Propanediol bis (2-mercaptoacetate), 3-mercapto-1,2-propanediol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate) Erythritol tetrakis (3-mercaptopropionate), glycerol (2-mercaptoacetate), glycerol tris (3-mercaptopropionate), 1,4-cyclohexanediol bis (2-mercaptoacetate), 1,4-cyclohexanediol bis Propionate), hydroxymethyl-sulfide bis (2-mercaptoacetate), hydroxymethyl-sulfide bis (3-mercaptopropionate), hydroxyethyl-sulfide (2-mercaptoacetate) Disulfide (3-mercaptopropionate), hydroxymethyl-disulfide (2-mercaptoacetate), hydroxymethyl-disulfide (3-mercaptopropionate), (2- Mercaptoethylester) thioglycolate and bis (2-mercaptoethylester) thiodipropionate, and aromatic thio compounds such as 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2- Benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, (Mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (Mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,4-tris 2,4-tris (mercaptoethyl) benzene, 2,5-toluene dithiol, 3,4-toluene dithiol, 1,4-naphthalene dithiol, 1,5-naphthalene dithiol, 2,7-naphthalene dithiol, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1 , 2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (Ethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 2,2'-dimercaptobiphenyl and 4,4'-dimercaptobiphenyl.

Preferred polythio compounds B) are the above-described types of polythioethers and polyester thiols. Particularly preferred polythio compounds B) are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bismercaptomethyl-1,4-dithiane, 3,3-tetrakis (mercaptomethylthio) propane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, 4,7-dimercaptomethyl 1,1-dimercapto-3,6,9-trithiandecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiandecane, trimethylol (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptoacetate) and pentaerythritol tetrakis (3-mercaptopropionate )to be.

The sulfur-containing hydroxy compound is also suitable as component B) which is reactive with respect to the isocyanate group. Examples thereof include simple mercapto-alcohols such as 2-mercaptoethanol, 3-mercaptopropanol, 1,3-dimercapto-2-propanol, 2,3-dimercaptopropanol and dithioerythritol, Di (2-hydroxyethyl) sulfide, 1,2-bis (2-hydroxyethylmercapto) ethane, bis -2,5-diol or a sulfur-containing diol having a polyester-urethane, polythioester-urethane, polyester-thiourethane or polythioester-thiourethane structure of the type mentioned in EP-A 1 640 394 .

Those having low molecular weight hydroxy- and / or amino-functional components, i.e. those having a molecular weight range of from 60 to 500, preferably from 62 to 400, are also suitable for preparing isocyanate-reactive compounds in the preparation of light-resistant polyurethane compositions according to the invention B).

These include, for example, simple monofunctional or polyfunctional alcohols having 2 to 14, preferably 4 to 10 carbon atoms, such as 1,2-ethanediol, 1,2- and 1,3-propanediol, , Pentane diol, hexane diol, heptane diol and octane diol, 1,10-decane diol, 1,2- and 1,4-cyclohexane diol, 1,4-cyclohexane dimethanol, 4,4 '- 1,1,1-trimethylolethane, 1,2,6-hexanetriol, 1,1,1-trimethylol propane, 1,1,1-trimethylol propane, , 2,2-bis (hydroxymethyl) -1,3-propanediol, bis- (2-hydroxyethyl) -hydroquinone, 1,2,4- and 1,3,5-trihydroxycyclohexane or 1,3,5-tris (2-hydroxyethyl) isocyanurate.

Examples of suitable low molecular weight amino functional compounds include aliphatic and cycloaliphatic amines and amino alcohols having an amino group bonded as a primary and / or secondary group, such as cyclohexylamine, 2-methyl-1,5-pentanediamine , Diethanolamine, monoethanolamine, propylamine, butylamine, dibutylamine, hexylamine, monoisopropanolamine, diisopropanolamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, iso (Aminopropyl) piperazine, aminoethylpiperazine, 1-aminoethylpiperazine, 1-ethylhexylamine, diethylenetriamine, diaminocyclohexane, hexamethylenediamine, methyliminobispropylamine, iminobispropylamine, bis Diaminocyclohexane, triethylenetetramine, tetraethylenepentamine, 1,8-p-diaminomethane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl ) Methane, bis (4-amino-3,5-dimethylcyclohexyl) methane, bis (4-amino-2,3,5-trimethylcyclohexyl) Bis (4-aminocyclohexyl) ethane, 1,1-bis (4-aminocyclohexyl) butane, 2,2-bis Aminocyclohexyl) butane, 1,1-bis (4-amino-3-methylcyclohexyl) ethane, 2,2- (4-amino-3,5-dimethylcyclohexyl) propane, 2,2-bis (4-amino-3,5-dimethylcyclohexyl) ) Butane, 2,4-diaminodicyclohexylmethane, 4-aminocyclohexyl-4-amino-3-methylcyclohexylmethane, 4-amino-3,5-dimethylcyclohexyl- Cyclohexylmethane and 2- (4-aminocyclohexyl) -2- (4-amino-3-methylcyclohexyl) methane.

Examples of aromatic polyamines, in particular diamines, having a molecular weight of less than 500, suitable compounds B) which are reactive towards isocyanates are 1,2- and 1,4-diaminobenzenes, 2,4- and 2,6- diaminotoluenes, 2 , 4'- and / or 4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 4,4 ', 4 "-triaminotriphenylmethane, 4,4'-bis- ) Diphenylmethane or 1-methyl-2-methylamino-4-aminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, Diaminobenzene, 1,3,5-trimethyl-2,4-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene, 3,5,3 ' Tetraethyl-4,4'-diaminodiphenylmethane, 3,5,3 ', 5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,5-diethyl- '-Diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diisopropyl-4,4'-diaminodiphenylmethane, , 6-diamino-3-isopropylbenzene, polyphenylpolymethylene polyamines liquid Mixtures obtainable, for example, by condensation of aniline and formaldehyde in a known manner, and any desired mixtures of such polyamines. In this connection, for example, 1-methyl-3,5-diethyl -2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diaminobenzene in a weight ratio of 50:50 to 85:15, preferably 65:35 to 80:20 Especially mentioned.

Low molecular weight amino functional polyethers having a molecular weight of less than 500 may also be used. They are, for example, those having primary and / or secondary, aromatic or aliphatic bonded amino groups, the amino groups of which are optionally bonded to the polyether chain via urethane or ester groups and which, for the preparation of high molecular weight aminopolyethers Can be obtained by a known method as described.

The sterically hindered aliphatic diamines having two amino groups bonded as secondary radicals can optionally be used as component B) which is reactive towards isocyanate groups, for example aliphatic and / or cycloaliphatic diamines known from EP-A 0 403 921 And maleic acid esters or fumaric acid esters, the bis-adducts of acrylonitrile on isophorone diamine which can be obtained according to the teachings of EP-A 1 767 559 or the aliphatic and / or cycloaliphatic diisocyanates described in DE-A 19 701 835, Or a hydrogenation product of a Schiff base obtainable from a cycloaliphatic diamine and a ketone such as diisopropyl ketone.

Preferred reaction partners B) for the polyisocyanate mixture A) are the polymeric polyether polyols, polyester polyols and / or aminopolyethers described above, the polythio compounds, the low molecular weight aliphatic and cycloaliphatic polyfunctional alcohols and the low molecular weight polyfunctional Amine, particularly a sterically hindered aliphatic diamine having two amino groups bonded as a secondary group.

Preferred mixtures of components B) which are reactive towards isocyanate groups and exemplified above are also suitable as reaction partners for the polyisocyanate mixture A). The pure polyurethane composition is obtained entirely by using the hydroxy-functional component B), and the pure polythiourethane is obtained entirely by using the thio compound B), and the pure polyurea composition is obtained by using the polyamine B) entirely, By using an appropriate mixture of amino alcohols, mercapto-alcohols or hydroxy-, mercapto and amino-functional compounds as component B), it is possible to adjust the equivalent ratio of urethane to thiourethane and / Can be prepared.

The polyisocyanate component A) is in principle used as the only polyisocyanate component in the manufacture of light-resistant polyurethane compositions. Theoretically, however, the polyisocyanate component A) can be combined with any desired additional non-solvent low-monomer polyisocyanates such as uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazine Known hexamethylene-diisocyanate (HDI) based lacquer polyisocyanates having a lean structure, such as those described in J. Prakt. Chem. 336 (1994) 185-200 and EP-A 0 798 299, EP-A 0 693 512 and EP-A 1 484 350, a solution of a cycloaliphatic polyisocyanate in a low viscosity HDI polyisocyanate, EP -A 0 047 452 and EP-A 0 478 990, which can be obtained by dimerization and / or trimerization from HDI and isophorone diisocyanate (IPDI), or EP-A 0 336 205 May also be used in admixture with polyester-modified HDI polyisocyanates of known type.

Regardless of the nature of the starting materials chosen, the reaction of component B), which is reactive with the polyisocyanate mixture A) and the isocyanate group, in the process according to the invention is carried out in such a way that the equivalence ratio of the groups which are reactive towards isocyanate groups to isocyanates is from 0.5: : 1, preferably 0.7: 1 to 1.3: 1, particularly preferably 0.8: 1 to 1.2: 1.

In addition to the abovementioned starting components A) and B), further auxiliaries and additives C) may optionally be used in the present invention, for example catalysts, blowing agents, surface active agents, UV stabilizers, foam stabilizers, antioxidants, , Fillers and pigments.

For example, conventional catalysts known in the polyurethane chemistry can be used to facilitate the reaction. Examples of such catalysts include tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine, pyridine, methylpyridine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, (Dimethylaminopropyl) urea, N-methyl- and N-ethylmorpholine, N-cocomorpholine, N-cyclohexylmorpholine, N, N, N ' , N'-tetramethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N' Dimethylpiperazine, N, N'-dimethylpiperazine, N-methyl-N'-dimethylaminopiperazine, 1,8-diaza- (5.4.0) undec-7-ene (DBU), 1,2-dimethylimidazole, 2-methylimidazole, N, N- dimethylimidazole- Diazabicyclo- (2,2,2) -octane, bis- (N, N-dimethylaminoethyl) adipate; Alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyl-diethanolamine, dimethylaminoethanol, 2- (N, N-dimethylaminoethoxy) "- tris- (dialkylaminoalkyl) hexahydrotriazine such as N, N ', N" -tris- (dimethylaminopropyl) -s-hexahydrotriazine and / or bis (dimethylaminoethyl) ether; Inorganic and / or organic compounds of metal salts, such as iron, lead, bismuth, zinc and / or tin (present in the oxidation of conventional metals), such as iron (II) chloride, iron (III) chloride and bismuth (III). Bismuth (III) octoate, bismuth (III) neodecanoate, zinc chloride, zinc 2-ethyl caproate, tin (II) octoate, tin (II) ) Ethyl caproate, tin (II) palmitate, dibutyltin (IV) dilaurate (DBTL), dibutyltin (IV) dichloride or lead octoate; Amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine; Tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; Alkali metal hydroxides such as sodium hydroxide and alkali metal alcoholates such as sodium methylate and potassium isopropylate and alkali metal salts of long chain fatty acids having 10 to 20 C atoms and optionally having side chain OH groups.

Preferred catalysts C) used are tertiary amines of the type described above and bismuth and tin compounds.

The above-exemplified catalysts can be used in the preparation of the light-resistant polyurethane, polythiourethane and / or polyurea compositions according to the invention, either alone or in any desired combination with one another, Is used in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 2% by weight in terms of the total amount of the catalyst used.

A transparent compression-molded part having a high refractive index is preferably produced by the method according to the present invention. However, by adding a suitable foaming agent, a foamed molded article can be obtained, if necessary. Suitable blowing agents are, for example, volatile organic substances such as acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorotrifluoromethane Or dichlorodifluoromethane, butane, hexane, heptane or diethyl ether and / or a dissolved inert gas such as nitrogen, air or carbon dioxide.

Usable chemical blowing agents C), i.e. blowing agents which form gaseous products due to, for example, reaction with isocyanate groups, are, for example, water, compounds containing water-containing compounds, carboxylic acids, tertiary alcohols such as t- , Carbamates, such as those described in EP-A 1 000 955, specifically on the second side, lines 5 to 31 and on the third side of lines 21 to 42, carbamates, carbonates such as ammonium carbonate and / ≪ / RTI > ammonium bicarbonate and / or guanidine carbamate. The foaming action may also be achieved by adding a compound which decomposes with the decomposition of a gas, e.g. nitrogen, at a temperature above room temperature, such as an azo compound, for example azodicarboxamide or azoisobutyric acid nitrile. Other examples of blowing agents and details of the use of blowing agents are described in Kunststoff-Handbuch, volume VII, Vieweg und Hoechtlen, Carl-Hanser-Verlag, Munich 1996, for example on pages 108 and 109, 455 < / RTI > and Sections 507 to 510, respectively.

The foaming action may also be achieved by adding a compound which decomposes with the decomposition of a gas, e.g. nitrogen, at a temperature above room temperature, such as an azo compound, for example azodicarboxamide or azoisobutyric acid nitrile. Other examples of blowing agents and details of the use of blowing agents are described in Kunststoff-Handbuch, volume VII, Vieweg und Hoechtlen, Carl-Hanser-Verlag, Munich 1996, for example on pages 108 and 109, 455 < / RTI > and Sections 507 to 510, respectively.

According to the invention, surface active additives C) can also be used together as emulsifiers and foam stabilizers. Examples of suitable emulsifiers are castor oil sulfonate or sodium salts of fatty acids and salts of fatty acids and amines, such as diethylamine oleate or diethanolamine stearate. Alkali metal or sulfonic acids such as dodecylbenzenesulfonic acid, fatty acids such as ricinoleic acid, or ammonium salts of polymeric fatty acids or ethoxylated nonylphenols can also be used together as surface active additives.

Suitable foam stabilizers are specifically known, preferably water-soluble, polyether siloxanes such as those disclosed in US-A 2 834 748, DE-A 1 012 602 and DE-A 1 719 238. Polysiloxane / polyoxyalkylene copolymers obtainable according to DE-A 2 558 523, which is branched through allophanate groups, are also suitable foam stabilizers.

These emulsifiers and stabilizers, which may optionally be used in combination with the process according to the invention, can be used both alone and in any desired mixtures with one another.

The shaped bodies obtained from the polyurethane compositions which can be prepared and used according to the invention are characterized in that they are already very stable in their own light, without the addition of the corresponding stabilizers. Nonetheless, known types of UV protecting agents (light stabilizers) or antioxidants can optionally be used in the preparation, optionally as further auxiliaries and additives C).

Suitable UV stabilizers C) are, for example, piperidine derivatives such as 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy- Pentamethylpiperidine, bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl ) Sebacate, methyl- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis- (2,2,6,6-tetramethyl-4-piperidyl) (2,2,6,6-tetramethyl-4-piperidyl) dodecanedioate, benzophenone derivatives such as 2,4-dihydroxy-, 2-hydroxy-4- Hydroxy-4-dodecyloxy-, or 2,2'-dihydroxy-4-dodecyloxy-benzophenone, benzotriazole derivatives, For example, 2- (5-tert-butylphenyl) benzotriazole, 2- (5-tert-butylphenyl) benzotriazole, 2- Hydroxyphenyl) benzotriazole, 2- (5-dodecyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and 2- Ethyl-2'-ethoxy- or 4-methyl-4 '- (3-tert-butyl-5-propionic acid-2-hydroxyphenyl) benzotriazole with polyethylene glycol 300, -Methoxyoxanilide, salicylic acid esters such as phenyl salicylic acid ester, 4-tert-butylphenyl ester salicylic acid and 4-tert-octylphenyl ester salicylate, cinnamic acid ester derivatives such as? -Cyano-? Cyano-β-methyl-4-methoxycinnamic acid butyl ester, α-cyano-β-phenyl cinnamic acid ethyl ester and α-cyano-β-phenyl cinnamic acid isooctyl ester, or On malonic acid Stearic derivatives such as 4-methoxybenzylidenemalonic acid dimethyl ester, 4-methoxybenzylidenemalonic acid diethyl ester and 4-butoxybenzylidenemalonic acid dimethyl ester. Such light stabilizers may be used alone or in any desired mixtures with one another.

Suitable antioxidant C) is, for example, a known sterically hindered phenol such as 2,6-di-tert-butyl-4-methylphenol (Ionol), pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethyleneglycol bis (3-tert- butyl-4-hydroxy-5-methylphenyl) propionate, 2,2'-thio-bis (4-methyl- - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), which may be used alone or in any desired mixture with each other.

Further auxiliary substances and additives C) which may optionally be used together are, for example, cell regulators of the type known per se, for example paraffin or fatty alcohols, known flame retardants such as tris-chloroethyl phosphate, ammonium phosphate or Polyphosphates, fillers such as barium sulfate, diatomaceous earth, carbon black, washed white china or tempered glass fiber. Finally, internal mold release agents, dyes, pigments, hydrolytic stabilizers, and also known antifungal and antibacterial agents, as such, may optionally be used in combination with the process according to the invention.

Said auxiliary substances and additives C) which may optionally be used together can be mixed with the polyisocyanate component A) and / or with component B) which is reactive towards isocyanate groups.

In order to prepare a light-resistant molded article according to the present invention from a polyurethane composition, the low-monomer polyisocyanate A) is mixed with the component B) which is reactive to the isocyanate group, optionally with the aid and the additive C) By mixing in an unsolvated form in an equivalent ratio of isocyanate groups to groups reactive with isocyanate groups as described above and then by mixing the mixture in an open or closed mold by any desired method, For example, by means of a suitable low-pressure or high-pressure machine in the field of polyurethane technology, or by the RIM method at a temperature of from 40 to 180 DEG C, preferably from 50 to 140 DEG C, particularly preferably from 60 to 120 DEG C Under temperature, optionally up to 300 bar, preferably up to 100 bar, Preferably under a high pressure of 40 bar or less.

In this procedure, the polyisocyanate A) and optionally the starting component B) are preheated to a temperature of at least 40 DEG C, preferably at least 50 DEG C, particularly preferably at least 60 DEG C, to reduce viscosity and optionally to degas by applying a vacuum.

In principle, the shaped bodies produced from the polyurethane compositions which can be prepared and used according to the invention in this way can be removed from the mold after a short period of time, for example from 2 to 60 minutes. If appropriate, post-curing treatment may be followed at 50 to 100 占 폚, preferably at 60 to 90 占 폚.

In this way, compressed or foamed light and weatherable polyurethane bodies can be obtained which are characterized by high resistance to solvents and chemicals and excellent mechanical properties, in particular excellent heat distortion points at high temperatures, for example 90 [deg.] C.

Preferably, the low-monomer isocyanate aliphatic polyisocyanate A) is used to prepare a transparent compression-molded body. These transparent polyurethane bodies are suitable for a variety of different uses, for example in the manufacture of glass replacement glazings or as glass replacement glazing, for example as front, rear or side screens of a sun roof, vehicle or aircraft structure, and safety glass.

The polyurethane composition according to the invention is also particularly suitable as a transparent embedding material of optical, electronic or optoelectronic components, for example those used as solar modules, light emitting diodes or lenses or collimators, for example LED lamps or automotive headlamp assist lenses Do.

However, a particularly preferred field of use for the polyurethane compositions obtainable from the low-monomer isocyanate polyisocyanate A according to the invention is the production of plastic light-weight spectacle lenses with high refractive index and high Abbe number. The spectacle lens produced by the present invention is characterized by excellent mechanical properties, particularly hardness and impact strength, as well as excellent scratch resistance, and is easy to work and can be colored as required.

Example

Unless otherwise noted, all percent data below are based on weight.

The NCO content was determined by titration according to DIN EN ISO 11909.

OH was determined by titration according to the method of Part 2 of DIN 53240, and the acid value was determined according to DIN 3682.

The residual monomer content was determined by gas chromatography using an internal standard material in accordance with DIN EN ISO 10283.

All viscosity measurements were carried out in accordance with DIN EN ISO 3219 using a Fiji MCR 51 Rheometer from Anton Paar Germany GmbH (Germany).

The glass transition temperature Tg was measured by DSC (differential scanning calorimetry) using a Mettler DSC 12E (Mettler Toledo GmbH, Zijsen, Germany) at a heating rate of 20 占 폚 / min.

The Shore hardness was measured according to DIN 53505 using a Zwick 3100 Shore hardness tester (Zwick, Germany).

The refractive index and Abbe number were measured on an Abbe refractometer, Model B, available from Zeiss.

Starting compound

Polyisocyanate A1)

2,256 g (12 moles) of 1,3-bis (isocyanatomethyl) benzene (m-XDI) were reacted with 46.5 g (0.25 moles) of anhydrous pivalic acid by the method described in EP-A 0 157 088, ) And 18 g (1 mole) of water in the presence of 200 g of triethylphosphate to give a buret polyisocyanate. The excess m-XDI was then removed by thin-film distillation at a temperature of 150 DEG C under a pressure of 0.1 mabr. A highly viscous pale yellow resin was obtained.

NCO content: 21.1%

NCO functionality: 3.3

Monomer m-XDI: 0.3%

Viscosity (23 ° C): 182,000 mPas

Viscosity (60 ° C): 1,500 mPas

Polyisocyanate A2)

1.4 g (7 mmol) of tributylphosphine catalyst were added to 940 g (5.0 moles) of m-XDI under nitrogen at room temperature with stirring, then the mixture was heated to 60 占 폚. After about 1 hour, the NCO content of the mixture dropped to 26.4%, and the reaction was stopped by adding 1.3 g (7 mmol) of methyltoluenesulfonate and heating at 80 DEG C for 1 hour. After removing unreacted excess m-XDI by thin-film distillation at a temperature of 150 캜 under a pressure of 0.1 mbar, the polyisocyanate containing an isocyanurate group and a uretdione group was obtained in the form of a glassy, almost colorless resin Respectively.

NCO content: 17.4%

NCO functionality: 2.4

Monomer m-XDI: 0.2%

Viscosity (60 ° C): 6,800 mPas

Polyisocyanate A3)

XDI was trimerized using a 50% strength solution of tetrabutylphosphonium hydrogendifluoride in isopropanol / methanol (2: 1) as the catalyst by the method described in Example 4 of EP-A 0 962 455 And m-XDI polyisocyanate comprising an isocyanate group and an iminooxyadiazinedione group prepared by adding dibutyl phosphate to stop the reaction at an NCO content of 36% of the crude mixture. After removal of the unreacted m-XDI by thin-film distillation at a temperature of 150 캜 under a pressure of 0.1 mbar, a glassy solid resin having the following characteristic data was obtained.

NCO content: 20.4%

NCO functionality: 3.2

Monomer m-XDI: 0.1%

Viscosity (60 ° C): 8,500 mPas

Hydroxy-functional reaction partner B1)

A hydroxy-functional reaction partner B1) as a starting compound, a solventless polyester polyol prepared as disclosed in WO 2010/083958.

Viscosity (23 ° C): 19,900 mPas

OH: 628 mg KOH / g

Acid value: 2.2 mg KOH / g

OH functionality: 2.6

Average molecular weight: 243 g / mol (calculated from OH side)

Mercapto functional reaction partner B2)

Pentaerythritol tetrakis (3-mercaptopropionate) (= THIOCURE ^® PETMP, Brunauborg, Germany)

Equivalent: 122.2 g / SH equivalent

Examples 1 to 8 (Preparation of polyurethane embedding composition)

To prepare the reclaimed composition, the low-monomer polyisocyanate A) and the polyol component B) were preheated together (parts by weight) as shown in the following Table 1 to 60 DEG C (in each case the ratio of isocyanate groups to isocyanate groups , The mixture was homogenized for 1 minute at 3,500 rpm using a SpeedMixer DAC 150 FV (Hauschild, Germany), and then the open, unheated polypropylene < RTI ID = 0.0 > And injected manually into the mold. After curing for 24 hours at 70 DEG C in a drying cabinet, the test specimen (50 mm in diameter, 5 mm in height) was removed from the mold.

After a further 24 hours of curing at room temperature, the test specimens were tested for their mechanical and optical properties. Test results are also shown in the following table.

Claims (15)

Preheated to above 50 < 0 >C; (Isocyanatomethyl) benzene, 1,3-bis (isocyanatomethyl) benzene, 1,4-bis (isocyanatomethyl) benzene and 1,3-bis ≪ / RTI > is formed from two or more araliphatic diisocyanates; Of a solventless polyisocyanate component A) having an isocyanate group content of 11 to 21.5% by weight and a monomeric diisocyanate content of less than 0.8%
A method of use for the manufacture of a light resistant compacted or foamed polyurethane body. The method according to claim 1, wherein the polyisocyanate component A) has at least one structure selected from uretdione, allophanate, isocyanurate, iminooxyadinedione and burette. delete The polyisocyanate composition according to claim 1, wherein the polyisocyanate component A) is a polyisocyanate based on 1,3-bis (isocyanatomethyl) benzene having an isocyanate group content of 15 to 21% by weight and a monomeric diisocyanate content of less than 0.5% Lt; / RTI > A process as claimed in claim 1 or 2, characterized in that, in the preparation of the polyisocyanate component A), the aliphatic diisocyanate which is unreacted monomers is removed from the reaction product by extraction or thin-film distillation. 2. The method of claim 1, wherein the transparent, The method according to claim 6, wherein the polyurethane body is a glass replacement part. The method according to claim 6, wherein the polyurethane body is an optical, optoelectronic or electronic component. The method according to claim 8, wherein the component is an optical lens or a spectacle lens. 9. The method of claim 8, wherein the component is a light emitting diode. A) preheated to 50 DEG C or higher; (Isocyanatomethyl) benzene, 1,3-bis (isocyanatomethyl) benzene, 1,4-bis (isocyanatomethyl) benzene and 1,3-bis ≪ / RTI > is formed from two or more araliphatic diisocyanates; A solventless polyisocyanate component having an isocyanate group content of 11 to 21.5% by weight and a monomeric diisocyanate content of less than 0.8%
and
B) a reaction partner which is reactive towards isocyanate groups and has an average functionality of from 2.0 to 6.0
By the absence of the solvent,
While maintaining the equivalent ratio of isocyanate group to isocyanate reactive group to 0.5: 1 to 2.0: 1,
A method for manufacturing a light-resistant polyurethane body. 12. The composition according to claim 11, characterized in that as component B) there is used at least one compound selected from hydroxy-functional compounds, amino-functional compounds and mercapto-functional compounds having a number average molecular weight of 60 to 12,000 Way. The method according to claim 11, wherein at least one of (i) to (v) is used as component B).
(i) at least one selected from polyether polyols, polyester polyols, polycarbonate polyols and aminopolyethers having a number average molecular weight of 106 to 12,000.
(ii) a polythioether thiol.
(iii) polyester thiol.
(iv) a sulfur-containing hydroxy compound
(v) at least one selected from a low molecular weight, hydroxy-functional component and an amino-functional component having a number average molecular weight of 60 to 500; 12. A process as claimed in claim 11, wherein as component C) one or more selected from catalysts, UV stabilizers, antioxidants and mold release agents are used. The process according to claim 11, wherein the reaction of the reaction partner is carried out at a temperature of 180 ° C or less under a pressure of 300 bar or less.